CN103044360A - Method for synthetizing diglycidyl endomethylenetetrahydrophthalate - Google Patents
Method for synthetizing diglycidyl endomethylenetetrahydrophthalate Download PDFInfo
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- CN103044360A CN103044360A CN2013100174742A CN201310017474A CN103044360A CN 103044360 A CN103044360 A CN 103044360A CN 2013100174742 A CN2013100174742 A CN 2013100174742A CN 201310017474 A CN201310017474 A CN 201310017474A CN 103044360 A CN103044360 A CN 103044360A
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- PAQFVIDMNINYAX-YWTTYQRVSA-N C=C(CCCC1OC1)C(C1C=CC[C@@H]2C1)C2C(OCC1OC1)=O Chemical compound C=C(CCCC1OC1)C(C1C=CC[C@@H]2C1)C2C(OCC1OC1)=O PAQFVIDMNINYAX-YWTTYQRVSA-N 0.000 description 1
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Abstract
The invention discloses a method for synthetizing diglycidyl endomethylenetetrahydrophthalate. The method comprises the following steps of: 1, carrying out ring-opening reaction; 2, carrying out cyclization reaction. By the method, the diglycidyl endomethylenetetrahydrophthalate is obtained. The method has the advantages that the reaction time is short; a large quantity of energy sources can be reduced; the method is suitable for continuous industrial production; the yield of the product is high; the maximum yield is up to 90.29 percent; the epoxy value of the product is high; the highest epoxy value is up to 0.60; and the excessive epichlorohydrin and dichloromethane solvent added into the reaction process can be recycled and reused, so that the production cost is greatly reduced. The method is mainly used for preparing the diglycidyl endomethylenetetrahydrophthalate.
Description
Technical field
The present invention relates to a kind of synthetic method of interior methylene radical tetrahydrophthalic acid 2-glycidyl ester.
Background technology
Interior methylene radical tetrahydrophthalic acid 2-glycidyl ester (English name Diglycidyl Endomethylenetetrahydrophthalate is called for short NAG) is a kind of aliphatics 2-glycidyl ester type Resins, epoxy.Contain two ester bonds that above polarity is stronger in the aliphatic glycidyl ester based epoxy resin epoxy molecule, therefore have reactive behavior and the viscosifying power higher than ether type epoxy.It is little that this based epoxy resin has a molecular weight, viscosity is low, good manufacturability, reactive behavior is high, and the ordinary epoxy resin intermiscibility is good, and bounding force is higher than ordinary epoxy resin, electrical insulating property is good, have good anti-ultralow warm nature, characteristics such as surface gloss, light transmission and weathering resistance preferably are so interior methylene radical tetrahydrophthalic acid 2-glycidyl ester has good application prospect.But at present, the industrial method that does not have concrete synthetic interior methylene radical tetrahydrophthalic acid 2-glycidyl ester.
Summary of the invention
The invention provides a kind of method of synthetic interior methylene radical tetrahydrophthalic acid 2-glycidyl ester.
A kind of method of synthetic interior methylene radical tetrahydrophthalic acid 2-glycidyl ester, specifically finish according to the following steps: one, ring-opening reaction: at first Nadic anhydride and epoxy chloropropane are mixed, be heated to 80 ℃ ~ 150 ℃ from room temperature behind the mixing, then add deionized water and phase-transfer catalyst, and at 80 ℃ ~ 150 ℃ lower reaction 1h ~ 2h of temperature, namely finish ring-opening reaction; Two, cyclization: at first the reaction product with step 1 is cooled to room temperature, then add methylene dichloride and massfraction and be 20% ~ 40% sodium hydroxide solution, reaction 0.5h ~ 2h under temperature is 50 ℃ ~ 60 ℃, standing demix, then adopt methylene dichloride to extract, merge the organic layer that extraction obtains, then vacuum tightness for-0.09MPa ~-0.12MPa and temperature are under 50 ℃ ~ 90 ℃ conditions organic phase to be carried out underpressure distillation, underpressure distillation namely obtains interior methylene radical tetrahydrophthalic acid 2-glycidyl ester till extremely distillating without cut;
The mol ratio of the Nadic anhydride described in the step 1 and epoxy chloropropane is 1:(2 ~ 4); The mol ratio of the Nadic anhydride described in the step 1 and deionized water is 1:(1 ~ 4); The mol ratio of the Nadic anhydride described in the step 1 and phase-transfer catalyst is (40 ~ 60): 1;
The volume ratio of the epoxy chloropropane described in the methylene dichloride described in the step 2 and the step 1 is (0.9 ~ 1.1): 1; Massfraction described in the step 2 is that sodium hydroxide in 20% ~ 40% the sodium hydroxide solution and the mol ratio of the Nadic anhydride described in the step 1 are (2 ~ 4): 1.
Advantage of the present invention: one, the reaction times short, can save mass energy, adapt to continuous suitability for industrialized production; Two, product yield is high, and interior methylene radical tetrahydrophthalic acid 2-glycidyl ester productive rate is 43.23% ~ 90.29%, and maximum output can reach 90.29%; The product oxirane value is high, and oxirane value is 0.30 ~ 0.60, and high epoxy value can reach 0.60; Three, the excessive epoxy chloropropane that adds in the reaction and methylene chloride can recycle and reuse, greatly reduce production cost.
Description of drawings
Fig. 1 is the infrared spectrogram of the interior methylene radical tetrahydrophthalic acid 2-glycidyl ester of test one preparation; Fig. 2 is the hydrogen nuclear magnetic resonance spectrogram of the interior methylene radical tetrahydrophthalic acid 2-glycidyl ester of test one preparation.
Embodiment
Embodiment one: present embodiment is a kind of method of synthetic interior methylene radical tetrahydrophthalic acid 2-glycidyl ester, specifically finish according to the following steps: one, ring-opening reaction: at first Nadic anhydride and epoxy chloropropane are mixed, be heated to 80 ℃ ~ 150 ℃ from room temperature behind the mixing, then add deionized water and phase-transfer catalyst, and at 80 ℃ ~ 150 ℃ lower reaction 1h ~ 2h of temperature, namely finish ring-opening reaction; Two, cyclization: at first the reaction product with step 1 is cooled to room temperature, then add methylene dichloride and massfraction and be 20% ~ 40% sodium hydroxide solution, reaction 0.5h ~ 2h under temperature is 50 ℃ ~ 60 ℃, standing demix, then adopt methylene dichloride to extract, merge the organic phase that extraction obtains, then vacuum tightness for-0.09MPa ~-0.12MPa and temperature are under 50 ℃ ~ 90 ℃ conditions organic phase to be carried out underpressure distillation, underpressure distillation namely obtains interior methylene radical tetrahydrophthalic acid 2-glycidyl ester till extremely distillating without cut.
The mol ratio of the Nadic anhydride described in the present embodiment step 1 and epoxy chloropropane is 1:(2 ~ 4); The mol ratio of the Nadic anhydride described in the present embodiment step 1 and deionized water is 1:(1 ~ 4); The mol ratio of the Nadic anhydride described in the present embodiment step 1 and phase-transfer catalyst is (40 ~ 60): 1.
The volume ratio of the epoxy chloropropane described in the methylene dichloride described in the present embodiment step 2 and the step 1 is (0.9 ~ 1.1): 1; Massfraction described in the present embodiment step 2 is that sodium hydroxide in 20% ~ 40% the sodium hydroxide solution and the mol ratio of the Nadic anhydride described in the step 1 are (2 ~ 4): 1.
The building-up reactions formula of the method for methylene radical tetrahydrophthalic acid 2-glycidyl ester was as follows in present embodiment was synthetic:
The present embodiment reaction times is short, can save mass energy, adapts to continuous suitability for industrialized production.
The present embodiment product yield is high, and interior methylene radical tetrahydrophthalic acid 2-glycidyl ester productive rate is 43.23% ~ 90.29%, and maximum output can reach 90.29%; Present embodiment product oxirane value is high, and oxirane value is 0.30 ~ 0.60, and high epoxy value can reach 0.60.
The excessive epoxy chloropropane that adds in the present embodiment reaction and methylene chloride can recycle and reuse, greatly reduce production cost.
Embodiment two: the difference of present embodiment and embodiment one is: the phase-transfer catalyst described in the step 1 is Tetrabutyl amonium bromide, tetrabutylammonium chloride, palmityl trimethyl ammonium chloride, benzyltriethylammoinium chloride or Dodecyl trimethyl ammonium chloride.Other are identical with embodiment one.
Embodiment three: present embodiment and one of embodiment one or twos' difference is: the mol ratio of the Nadic anhydride described in the step 1 and epoxy chloropropane is 1:(2.5 ~ 3.5).Other are identical with embodiment one or two.
Embodiment four: the difference of one of present embodiment and embodiment one to three is: the mol ratio of the Nadic anhydride described in the step 1 and deionized water is 1:(2 ~ 3).Other are identical with embodiment one to three.
Embodiment five: the difference of one of present embodiment and embodiment one to four is: the mol ratio of the Nadic anhydride described in the step 1 and phase-transfer catalyst is (45 ~ 55): 1.Other are identical with embodiment one to four.
Embodiment six: the difference of one of present embodiment and embodiment one to five is: the volume ratio of the epoxy chloropropane described in the methylene dichloride described in the step 2 and the step 1 is 1:1.Other are identical with embodiment one to five.
Embodiment seven: the difference of one of present embodiment and embodiment one to six is: the massfraction described in the step 2 is that sodium hydroxide in 30% the sodium hydroxide solution and the mol ratio of the Nadic anhydride described in the step 1 are (2.5 ~ 3.5): 1.Other are identical with embodiment one to five.
Adopt following verification experimental verification effect of the present invention:
Test one: a kind of method of synthetic interior methylene radical tetrahydrophthalic acid 2-glycidyl ester, specifically finish according to the following steps: one, ring-opening reaction: at first Nadic anhydride and epoxy chloropropane are mixed, be heated to 104 ℃ from room temperature behind the mixing, then add deionized water and phase-transfer catalyst, and at 110 ℃ of lower reaction 2h of temperature, namely finish ring-opening reaction; Two, cyclization: at first the reaction product with step 1 is cooled to room temperature, then add methylene dichloride and massfraction and be 30% sodium hydroxide solution, reaction 1h under temperature is 55 ℃, standing demix, then adopting methylene dichloride to extract, merge the organic phase that extraction obtains, is under 80 ℃ of conditions organic phase to be carried out underpressure distillation in vacuum tightness for-0.09MPa and temperature then, underpressure distillation namely obtains interior methylene radical tetrahydrophthalic acid 2-glycidyl ester till extremely distillating without cut.
The mol ratio of the Nadic anhydride described in this testing sequence one and epoxy chloropropane is 1:3; The mol ratio of the Nadic anhydride described in this testing sequence one and deionized water is 1:2; The mol ratio of the Nadic anhydride described in this testing sequence one and phase-transfer catalyst is 40:1; Phase-transfer catalyst described in this testing sequence one is Tetrabutyl amonium bromide.
The volume ratio of the epoxy chloropropane described in the methylene dichloride described in this testing sequence two and the step 1 is 1:1; Massfraction described in this testing sequence two is that sodium hydroxide in 30% the sodium hydroxide solution and the mol ratio of the Nadic anhydride described in the step 1 are 3:1.
Methylene radical tetrahydrophthalic acid 2-glycidyl ester productive rate is 88.48% in as can be known this test by detecting, and oxirane value is 0.56.
Adopt Fourier infrared spectrograph to detect the interior methylene radical tetrahydrophthalic acid 2-glycidyl ester of test one preparation, detected result as shown in Figure 1, Fig. 1 is the infrared spectrogram of the interior methylene radical tetrahydrophthalic acid 2-glycidyl ester of test one preparation, as shown in Figure 1 3063cm
-1Represent the C-H stretching vibration, 1664m
-1Represent the C=C stretching vibration, illustrated that C=C exists; 2980cm
-1Represent on the bridged ring-CH
2-antisymmetric stretching vibration, 2874cm
-1Represent on the bridged ring-CH
2-symmetrical stretching vibration, 1450cm
-1Represent on the bridged ring-CH
2The vibration of-symmetric curvature, 758cm
-1Represent on the bridged ring-CH
2-rocking vibration, the methylene radical in the description architecture on the bridged ring exists; 1742cm
-1Represent the C=O stretching vibration, 1253cm
-1Represent C (O)-O stretching vibration, illustrated that ester bond exists.
The interior methylene radical tetrahydrophthalic acid 2-glycidyl ester of testing a preparation is carried out magnetic resonance detection, detected result as shown in Figure 2, Fig. 2 is the hydrogen nuclear magnetic resonance spectrogram of the interior methylene radical tetrahydrophthalic acid 2-glycidyl ester of test one preparation, and its data are:
1H?NMR(CDCl
3)：δ6.27(m，2H，C=C-H)；4.37(m，2H，O-CH
2)；3.82(m，2H，O-CH
2)；3.55(m，2H，O-CH)；3.18(m，4H，-CH-)；2.82(m，2H，CH-CH
2)；2.61(m，2H，CH-CH
2)；1.50(m，1H，-CH
2-)；1.35(m，1H，-CH
2-).
The structural formula of testing as can be known the interior methylene radical tetrahydrophthalic acid 2-glycidyl ester of a preparation in conjunction with Fourier infrared spectrograph detected result and magnetic resonance detection detected result is:
Test two: this test with the difference of test one is: the mol ratio of the Nadic anhydride described in the step 1 and epoxy chloropropane is 1:2.Other are identical with test one.
Methylene radical tetrahydrophthalic acid 2-glycidyl ester productive rate is 66.94% in as can be known this test by detecting, and oxirane value is 0.49.
Test three: this test with the difference of test one is: the mol ratio of the Nadic anhydride described in the step 1 and epoxy chloropropane is 1:4.Other are identical with test one.
Methylene radical tetrahydrophthalic acid 2-glycidyl ester productive rate is 86.36% in as can be known this test by detecting, and oxirane value is 0.54.
Test four: this test with the difference of test one is: the phase-transfer catalyst described in the step 1 is tetrabutylammonium chloride.Other are identical with test one.
Methylene radical tetrahydrophthalic acid 2-glycidyl ester productive rate is 71.84% in as can be known this test by detecting, and oxirane value is 0.52.
Test five: this test with the difference of test one is: the phase-transfer catalyst described in the step 1 is palmityl trimethyl ammonium chloride.Other are identical with test one.
Methylene radical tetrahydrophthalic acid 2-glycidyl ester productive rate is 81.36% in as can be known this test by detecting, and oxirane value is 0.51.
Test six: this test with the difference of test one is: the phase-transfer catalyst described in the step 1 is benzyltriethylammoinium chloride.Other are identical with test one.
Methylene radical tetrahydrophthalic acid 2-glycidyl ester productive rate is 83.63% in as can be known this test by detecting, and oxirane value is 0.52.
Test seven: this test with the difference of test one is: the phase-transfer catalyst described in the step 1 is Dodecyl trimethyl ammonium chloride.Other are identical with test one.
Methylene radical tetrahydrophthalic acid 2-glycidyl ester productive rate is 78.86% in as can be known this test by detecting, and oxirane value is 0.50.
Test eight: this test with the difference of test one is: the mol ratio of the Nadic anhydride described in the step 1 and deionized water is 1:1.Other are identical with test one.
Methylene radical tetrahydrophthalic acid 2-glycidyl ester productive rate is 48.61% in as can be known this test by detecting, and oxirane value is 0.36.
Test nine: this test with the difference of test one is: the mol ratio of the Nadic anhydride described in the step 1 and deionized water is 1:3.Other are identical with test one.
Methylene radical tetrahydrophthalic acid 2-glycidyl ester productive rate is 77.94% in as can be known this test by detecting, and oxirane value is 0.53.
Test ten: this test with the difference of test one is: the mol ratio of the Nadic anhydride described in the step 1 and deionized water is 1:4.Other are identical with test one.
Methylene radical tetrahydrophthalic acid 2-glycidyl ester productive rate is 80.23% in as can be known this test by detecting, and oxirane value is 0.51.
Test 11: this test with the difference of test one is: the mol ratio of the Nadic anhydride described in the step 1 and phase-transfer catalyst is 50:1.Other are identical with test one.
Methylene radical tetrahydrophthalic acid 2-glycidyl ester productive rate is 72.52% in as can be known this test by detecting, and oxirane value is 0.52.
Test 12: this test with the difference of test one is: the mol ratio of the Nadic anhydride described in the step 1 and phase-transfer catalyst is 60:1.Other are identical with test one.
Methylene radical tetrahydrophthalic acid 2-glycidyl ester productive rate is 74.13% in as can be known this test by detecting, and oxirane value is 0.49.
Test 12: this test with the difference of test one is: the mol ratio of the Nadic anhydride described in the step 1 and phase-transfer catalyst is 60:1.Other are identical with test one.
Methylene radical tetrahydrophthalic acid 2-glycidyl ester productive rate is 74.13% in as can be known this test by detecting, and oxirane value is 0.49.
Test 13: this test with the difference of test one is: react down 2h 90 ℃ of temperature in the step 1.Other are identical with test one.
Methylene radical tetrahydrophthalic acid 2-glycidyl ester productive rate is 51.23% in as can be known this test by detecting, and oxirane value is 0.36.
Test 14: this test with the difference of test one is: react down 2h 120 ℃ of temperature in the step 1.Other are identical with test one.
Methylene radical tetrahydrophthalic acid 2-glycidyl ester productive rate is 79.86% in as can be known this test by detecting, and oxirane value is 0.50.
Test 15: this test with the difference of test one is: react down 2h 120 ℃ of temperature in the step 1.Other are identical with test one.
Methylene radical tetrahydrophthalic acid 2-glycidyl ester productive rate is 77.94% in as can be known this test by detecting, and oxirane value is 0.40.
Test 16: this test with the difference of test one is: react down 1h 110 ℃ of temperature in the step 1.Other are identical with test one.
Methylene radical tetrahydrophthalic acid 2-glycidyl ester productive rate is 63.34% in as can be known this test by detecting, and oxirane value is 0.50.
Test 17: this test with the difference of test one is: react down 1.5h 110 ℃ of temperature in the step 1.Other are identical with test one.
Methylene radical tetrahydrophthalic acid 2-glycidyl ester productive rate is 83.61% in as can be known this test by detecting, and oxirane value is 0.55.
Test 18: this test with test one difference is: the massfraction described in the step 2 is that sodium hydroxide in 30% the sodium hydroxide solution and the mol ratio of the Nadic anhydride described in the step 1 are 2.2:1.Other are identical with test one.
Methylene radical tetrahydrophthalic acid 2-glycidyl ester productive rate is 90.29% in as can be known this test by detecting, and oxirane value is 0.53.
Test 19: this test with test one difference is: the massfraction described in the step 2 is that sodium hydroxide in 30% the sodium hydroxide solution and the mol ratio of the Nadic anhydride described in the step 1 are 4:1.Other are identical with test one.
Methylene radical tetrahydrophthalic acid 2-glycidyl ester productive rate is 80.36% in as can be known this test by detecting, and oxirane value is 0.56.
Test 20: this test with the difference of test one is: react 0.5h in the step 2 under temperature is 55 ℃.Other are identical with test one.
Methylene radical tetrahydrophthalic acid 2-glycidyl ester productive rate is 85.54% in as can be known this test by detecting, and oxirane value is 0.50.
Test 21: this test with the difference of test one is: react 2h in the step 2 under temperature is 55 ℃.Other are identical with test one.
Methylene radical tetrahydrophthalic acid 2-glycidyl ester productive rate is 80.21% in as can be known this test by detecting, and oxirane value is 0.54.
Claims (7)
- One kind synthetic in the method for methylene radical tetrahydrophthalic acid 2-glycidyl ester, the method that it is characterized in that synthetic interior methylene radical tetrahydrophthalic acid 2-glycidyl ester is finished according to the following steps: one, ring-opening reaction: at first Nadic anhydride and epoxy chloropropane are mixed, be heated to 80 ℃ ~ 150 ℃ from room temperature behind the mixing, then add deionized water and phase-transfer catalyst, and at 80 ℃ ~ 150 ℃ lower reaction 1h ~ 2h of temperature, namely finish ring-opening reaction; Two, cyclization: at first the reaction product with step 1 is cooled to room temperature, then add methylene dichloride and massfraction and be 20% ~ 40% sodium hydroxide solution, reaction 0.5h ~ 2h under temperature is 50 ℃ ~ 60 ℃, standing demix, then adopt methylene dichloride to extract, merge the organic phase that extraction obtains, then vacuum tightness for-0.09MPa ~-0.12MPa and temperature are under 50 ℃ ~ 90 ℃ conditions organic phase to be carried out underpressure distillation, underpressure distillation namely obtains interior methylene radical tetrahydrophthalic acid 2-glycidyl ester till extremely distillating without cut;The mol ratio of the Nadic anhydride described in the step 1 and epoxy chloropropane is 1:(2 ~ 4); The mol ratio of the Nadic anhydride described in the step 1 and deionized water is 1:(1 ~ 4); The mol ratio of the Nadic anhydride described in the step 1 and phase-transfer catalyst is (40 ~ 60): 1;The volume ratio of the epoxy chloropropane described in the methylene dichloride described in the step 2 and the step 1 is (0.9 ~ 1.1): 1; Massfraction described in the step 2 is that sodium hydroxide in 20% ~ 40% the sodium hydroxide solution and the mol ratio of the Nadic anhydride described in the step 1 are (2 ~ 4): 1.
- 2. the method for a kind of synthetic interior methylene radical tetrahydrophthalic acid 2-glycidyl ester according to claim 1 is characterized in that the phase-transfer catalyst described in the step 1 is Tetrabutyl amonium bromide, tetrabutylammonium chloride, palmityl trimethyl ammonium chloride, benzyltriethylammoinium chloride or Dodecyl trimethyl ammonium chloride.
- According to claim 1 a kind of synthetic in the method for methylene radical tetrahydrophthalic acid 2-glycidyl ester, the mol ratio that it is characterized in that the Nadic anhydride described in the step 1 and epoxy chloropropane is 1:(2.5 ~ 3.5).
- According to claim 1 a kind of synthetic in the method for methylene radical tetrahydrophthalic acid 2-glycidyl ester, the mol ratio that it is characterized in that the Nadic anhydride described in the step 1 and deionized water is 1:(2 ~ 3).
- 5. according to claim 1,2,3 or 4 described a kind of synthetic in the methods of methylene radical tetrahydrophthalic acid 2-glycidyl esters, the mol ratio that it is characterized in that the Nadic anhydride described in the step 1 and phase-transfer catalyst is (45 ~ 55): 1.
- According to claim 1 a kind of synthetic in the method for methylene radical tetrahydrophthalic acid 2-glycidyl ester, the volume ratio that it is characterized in that the epoxy chloropropane described in the methylene dichloride described in the step 2 and the step 1 is 1:1.
- According to claim 1 or 6 described a kind of synthetic in the methods of methylene radical tetrahydrophthalic acid 2-glycidyl esters, it is characterized in that the massfraction described in the step 2 is that the mol ratio of sodium hydroxide and the Nadic anhydride described in the step 1 in 30% the sodium hydroxide solution is (2.5 ~ 3.5): 1.
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| CN106366639A (en) * | 2016-08-23 | 2017-02-01 | 无锡市永亿精密铸造有限公司 | Composite material used for ultrasonic sensors |
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| CN101054437A (en) * | 2007-04-29 | 2007-10-17 | 中国林业科学研究院林产化学工业研究所 | Method of preparing hydrogenated terpinene maleic anhydride glycidyl ester type epoxy resin |
| CN102617515A (en) * | 2012-03-02 | 2012-08-01 | 濮阳惠成电子材料股份有限公司 | Glycidyl ester type epoxy resin for electronic packaging and preparation process thereof |
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- 2013-01-17 CN CN2013100174742A patent/CN103044360A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101054437A (en) * | 2007-04-29 | 2007-10-17 | 中国林业科学研究院林产化学工业研究所 | Method of preparing hydrogenated terpinene maleic anhydride glycidyl ester type epoxy resin |
| CN102617515A (en) * | 2012-03-02 | 2012-08-01 | 濮阳惠成电子材料股份有限公司 | Glycidyl ester type epoxy resin for electronic packaging and preparation process thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106366639A (en) * | 2016-08-23 | 2017-02-01 | 无锡市永亿精密铸造有限公司 | Composite material used for ultrasonic sensors |
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Application publication date: 20130417 |